采用碱溶法去除牙科氧化锆陶瓷废弃粉体中的杂质

Removal of impurities from waste dental zirconia ceramic powder using an alkali dissolution method

  • 摘要: 背景 牙科氧化锆陶瓷在口腔修复领域得到了广泛应用。在制备牙科氧化锆修复体的数控加工阶段,氧化锆预烧结体超过80%的体积被加工掉成为废料粉体,造成资源巨大浪费,废弃氧化锆粉体的再生利用势在必行。目的 通过分析废弃氧化锆粉体中的杂质种类,提出一种可行的除杂方法。方法 废弃氧化锆粉体为从北京赢冠科技有限公司收集的爱尔创公司生产的白色氧化锆,数控设备所用刀具是带有金刚石涂层的碳化钨硬质合金。采用扫描电子显微镜观察废弃氧化锆粉体的微观形貌和聚集状态,并采用X射线能谱仪对粉体的化学成分进行表征。采用热重分析对碳化钨和金刚石的氧化温度进行初步确认。在不同温度下处理碳化钨,对其氧化过程进行定量分析,同时采用XRD对不同温度下处理的碳化钨进行物相分析,通过氧化后的物相组成确定氧化制度。氧化钨的溶解试验在水热反应釜中进行,将700℃高温处理后的碳化钨粉体与氨水在不同温度及不同时间下反应,使氧化钨生成可溶性的钨酸铵,通过抽滤、水洗和干燥,测得氧化钨的去除率,以此判断去除氧化钨的最佳工艺条件。将废弃氧化锆粉体在700℃高温下处理2 h 后,与0.3 N氨水在水热反应釜中于120℃下反应6 h,通过抽滤、水洗和干燥,得到去除杂质后的粉体。采用X射线荧光仪对除杂后的粉体与原始粉体的元素组成进行分析,以判断除杂效果。结果 通过对废弃粉体进行扫描电镜观察并对所选区域进行光电子能谱元素扫描,结合X-射线荧光分析结果,判断废弃氧化锆粉体中除含有初始氧化锆粉饼的固有元素Zr、Y、Hf 外,有W元素存在,这是数控设备所使用的碳化钨刀具的磨损所致。针对废弃氧化锆粉体中含有的碳化钨和金刚石杂质,采用热处理结合碱溶工艺去除。热重曲线表明,高温下金刚石先于碳化钨氧化,且金刚石完全氧化时的温度低于碳化钨完全氧化时的温度,因此采用碳化钨的氧化制度可以保证金刚石完全氧化。通过对碳化钨的氧化过程进行定量分析和物相测试,表明采用700℃下保温2 h 是比较合理的高温氧化处理工艺。氧化处理后生成的氧化钨通过水热碱溶工艺去除。氧化钨的去除率随着反应温度的提高而不断增加,设置8 h 反应时间,发现在120℃下反应8 h 后,氧化钨的去除率可以达到100%。考虑到减少反应时间,有利于节能及降低处理成本,对水热反应时间进行了优化,在120℃条件下发现反应6 h 后,氧化钨去除率达到100%,进一步确定了氧化钨的合理碱溶条件为120℃下反应6 h。将废弃氧化锆粉体先在700℃下保温2 h 进行氧化处理,再将处理后的粉体与0.3N氨水在反应釜中120℃下反应6 h,得到的除杂后的氧化锆粉体中碳化钨已经完全除去,而氧化锆粉体中本征成分的含量基本无变化。结论 合适的热处理工艺是在700℃下保温2 h,合适的碱溶条件是在120℃下在反应釜中反应6 h,可以有效去除废弃氧化锆粉体中的杂质。

     

    Abstract: Background Dental zirconia ceramics are widely used in the field of oral restoration. During the CNC machining stage of dental zirconia restorations, over 80% of the volume of the zirconia pre-sintered blocks is removed as waste powder, resulting in significant resource waste. Therefore, the recycling of waste zirconia powder is imperative. Objective Impurity removal is a crucial step in the recycling process of waste zirconia powder, yet there is limited research reported. This paper analyzes the types of impurities in waste zirconia powder and proposes a feasible method for impurity removal.Methods The waste zirconia powder used was ST zirconia produced by Upcera, collected from Beijing Yingguan Technology Co., Ltd. The CNC equipment utilized diamond-coated tungsten carbide tools. The microscopic morphology and aggregation state of the waste zirconia powder were observed using scanning electron microscopy (SEM), and its chemical composition was characterized by energy-dispersive Xray spectroscopy (EDS). Thermogravimetric analysis (TG-DSC) was employed to preliminarily determine the oxidation temperatures of tungsten carbide and diamond. The oxidation process of tungsten carbide was quantitatively analyzed at different temperatures, and X-ray, diffraction (XRD) was used for phase analysis of tungsten carbide treated at various temperatures, and the oxidation protocol was established based on the phase composition after oxidation. The dissolution test of tungsten oxide was conducted in a hydrothermal reactor. Tungsten carbide powder after high-temperature treatment at 700°C was reacted with ammonia solution at different temperatures and durations to form soluble ammonium tungstate. The removal rate of tungsten oxide was measured through suction filtration, washing, and drying to identify the optimal process conditions. The waste zirconia powder was treated at 700°C for 2 hours, then reacted with 0.3N ammonia solution in a hydrothermal reactor at 120°C for 6 hours. The impurityremoved powder was obtained via suction filtration, washing, and drying. The elemental compositions of the purified powder and the original powder were analyzed using X-ray fluorescence (XRF) to evaluate the impurity removal effect. Results SEM observation, EDS elemental mapping of selected areas, and XRF analysis confirmed that, in addition to the inherent elements of the original zirconia blanks (Zr, Y, Hf), the waste zirconia powder contained W, attributed to wear from the tungsten carbide tools used in CNC machining. To remove the tungsten carbide and diamond impurities, a combined process of heat treatment and alkaline leaching was adopted. TG-DSC curves indicated that diamond oxidizes prior to tungsten carbide at high temperatures, and the complete oxidation temperature of diamond is lower than that of tungsten carbide. Therefore, adopting the oxidation protocol for ,tungsten carbide ensures complete oxidation of diamond. Quantitative analysis and phase testing of the tungsten carbide oxidation process demonstrated that holding at 700°C for 2 hours is a reasonable high-temperature oxidation treatment. The tungsten oxide generated after oxidation was removed by hydrothermal alkali dissolution. The removal rate of tungsten oxide increased with higher reaction temperature. At a reaction time of 8 hours, a 100% removal rate was achieved at 120℃. To reduce reaction time for energy savings and lower processing costs, the hydrothermal reaction time was optimized. At 120℃, a 100% removal rate was attained after 6 hours of reaction. Thus, the optimal alkali dissolution conditions for tungsten oxide were determined to be 120℃ for 6 hours.After treating the waste zirconia powder at 700°C for 2 hours followed by reaction with 0.3N ammonia solution at 120°C for 6 hours in a reactor, the purified zirconia powder showed complete removal of tungsten carbide, while the content of intrinsic components in the zirconia powder remained unchanged. Conclusion For the waste powder generated during the manufacturing process of dental zirconia restorations, this paper proposes a combined method of heat treatment and alkaline leaching for impurity removal. The results indicate that the suitable heat treatment condition is holding at 700° C for 2 hours, and the appropriate alkaline leaching condition is reacting in a reactor at 120°C for 6 hours. This method can effectively remove impurities from waste zirconia powder, providing a reference for the recycling of waste zirconia powder.

     

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